Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014

ISSN 1583-1078 p. 23-36

Application of Simplified Anaerobic Digestion Models (SADMs) for

Studying the Biodegradability and Kinetics of Cow Manure at Ambient
Temperature

Yusuf O.L. MOMOH1* and Benedict ANYATA2

1Department of Civil and Environmental Engineering, University of Port-Harcourt, Choba,

P.M.B 5323 Rivers State, Nigeria.
2
Department of Civil Engineering, University of Benin, P.M.B 1154,
Benin City, Edo State, Nigeria.
E-mails: yusuf.momoh@uniport.edu.ng; bufanyat_a@yahoo.co.uk
*
Corresponding author: +2348035386779

Abstract
The application of a set of simplified anaerobic digestion models (SADMs)
to describe the anaerobic biodegradability and kinetics of cow manure at
ambient temperature was conducted in this study. It was observed that the
Hills based biogas yield rate model was the most appropriate in describing
biogas yield rate from cow manure. Parameter estimation revealed that the
half saturation constant expressed as acidified substrate and volatile solids
(VS) equivalent were 0.163g/l and 21.9g VS/l respectively while the
maximum biogas yield rate was estimated to be 1.957ml/g VS/day. The
coefficient of acidogenic bacteria adaptation (n) and coefficient of
acetogenic/methanogenic bacterial cooperativity (m) were estimated to be
1.28 and 0.65 respectively. The poor cooperativity amongst the
acetogenic/methanogenic bacterial species can be attributed to poor
adaptation, possibly due to interaction between ammonia and volatile fatty
acids. In addition, the biodegradability and recalcitrance was estimated to be
0.42 and 0.433 respectively, while hydrolysis/acidogenesis was identified as
the rate limiting step.

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

Keywords
Anaerobic; Biogas Yield; Cow Manure; Ambient Temperature;
Biodegradability; Saturation Constants; Kinetic Models; Performance.

Introduction

In an attempt to improve the living standard of developing countries, one hundred and
eighty nine countries (189) countries met at the United Nations (UN) headquarters in
September 2000 and agreed on an eight goal communiqu called the millennium development
goals (MDGs). These goals comprised (i) eradication of extreme poverty and hunger; (ii)
achieve universal primary education; (iii) promote gender equality and empower women; (iv)
reduce child mortality (v) improve maternal health; (vi) combat HIV/AIDS, malaria and other
diseases; (vii) ensure environmental sustainability and (viii) achieving global partnership for
sustainable development [1]. These goals which are expected to be met by 2015 have been
faced with series of challenges especially the problems of inadequate energy sources, a fact
which has been identified by Mshandete and Parawira [2] who recognized the availability of
sustained energy access as a major prerequisite for attainment of the millennium development
goals especially in sub-Saharan Africa.
Globally, more than 1.6 million people live without access to electricity while majority
of the poor world live in sub-Saharan Africa with about 60-70% of the most populous sub-
Saharan country having no access to electricity thus, relying strongly on wood fuel as the
predominant energy source [3,4]. Because of the relevance of energy access in the attainment
of the millennium development goals, the need to diversify energy sources has received
encouragement in many developing countries and the utilization and adoption of domestic
biogas technology has been identified as having the potentials of supporting energy services
and also contributes to meeting the needs of the millennium development goals [2].
Domestic biogas technology produces useful fuel (biogas) rich in methane that can be
utilized for cooking and heating purposes thus, contributing to hunger eradication. Also, the
bio-slurry is a potent organic fertilizer which can reduce the use of chemical fertilizer thus,
contributing to improve agricultural production and food security. In the area of sanitation,
domestic biogas technology can promote environmental sustainability by reducing

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 Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014
ISSN 1583-1078 p. 23-36

environmental pathogens and encouraging conservation of resources which generally support

the ideas of the millennium development goal.
Traditionally, cow manure is the predominant feedstock used in rural community for
domestic biogas production [5]. Though, cow manure is rich in methanogens necessary for
methane production, its high lignin content and nitrogen content tend to militate against
effective biogas production. Also, it has been reported that, the digestion of cow manure
results in a complex biochemical interaction of free ammonia, volatile fatty acids which are
both by product of the anaerobic process that produces an inhibited steady state
phenomenon. In this condition, anaerobic digestion proceeds stably but with lower methane
yield [6]. In addition to this phenomenon, ammonia has been established to inhibit
acetoclastic methanogenesis. Gallert and Winter [7] reported that free ammonia of 560568
mg NH3 N/l caused a 50% inhibition of methanogenesis at pH of 7.6 under thermophilic
condition. Another study on cattle manure at thermophilic temperature also indicated that free
ammonia above 700 mg NH3 N/l resulted in a poor treatment performance at a pH of 7.47.9
[8].
Thus, in order to appropriately understand the anaerobic degradation kinetics of cow
manure, adequate model testing and validation is required. Angelidaki [9] reported that many
of the existing substrate utilization models that are based on Monod growth models are
incapable of describing the kinetics of biogas production from cow manure and afterwards
developed a complex model that accounted for hydrolysis, acidogenesis, acetogenesis,
methanogenesis, free ammonia and volatile fatty that could appropriately describe the kinetics
of biogas production from cow manure. Moreover, with the development of anaerobic
digestion model No. 1(ADM 1), researchers have been able to evaluate the anaerobic
digestion of cow manure, though with some complications and alteration of the default kinetic
parameter associated with ADM 1 [10].
The utilization of complex models to assess anaerobic digestion of cow manure can be
very complicated and time consuming, hence, the need for simplified, generalized models for
evaluating kinetics of biogas production from complex biomass cannot be overemphasized.
Although, simplified substrate utilization kinetic models based on Contois growth model have
previously been employed for assessing the kinetics and biodegradability of cow manure [11,
12], these models depended strongly on the ability to measure the bacteria biomass volatile
suspended solids which can be very difficult procedure because of the difficulty in

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

differentiating between bacteria biomass volatile solids and complex biomass volatile solids
[13]. In this research, the application of simplified kinetic models as developed by Momoh et
al. [14] was applied in studying the kinetics and biodegradation of cow manure.
The aim of the research was focused on determining the kinetics and biodegradability
parameters of cow manure undergoing anaerobic digestion at ambient temperature conditions
using a set of simplified anaerobic digestion models (SADMs). These parameters would
provide sufficient information about the anaerobic bacterial behaviour and characteristic of
cow manure utilized in anaerobic digestion.

Material and Method

Cow manure utilized in this research was obtained from abattoir situated at Choba
community of Rivers State, Nigeria. About 1000g of cow manure was sun dried for 20days to
facilitate its measurement. A weighing balance (Mettler, model PN163) manufactured in
Switzerland with specification range between 0.1mg and 160g was utilized for mass
measurements. Crushing of cow manure using mortar and pestle preceded weighing of the
cow manure. The crushed cow manure was loaded into batch digesters (buchner flasks)
labeled A1, A2, A3, A4, A5, A6, A7 and A8 comprising total solid concentration of 2, 3, 4, 5,
6, 7, 8 and 9% respectively. The digesters were set-up as described by Momoh and
Nwagoazie [15] and set-ups were conducted in duplicates. The volatile solids content of the
cow manure were determined before the digestion process commenced according to APHA
[16] using a muffle furnace, Carbolite model LMF 4 manufactured in England. Similarly, the
carbon to nitrogen ratio of the feedstock was determined in accordance with APHA [16].
The cow manure was subsequently loaded into Buchner flasks and corked to exclude
air as described by Momoh and Nwagoazie [15]. The digesters were allowed to run
anaerobically for a period 35 days and agitated twice daily at an average ambient temperature
of 2830C. Water displacement method was used to measure biogas produced. The displaced
water was saturated brine solution which prevented the dissolution of carbon dioxide in the
water while, biogas produced was analyzed for methane content using Gas Chromatography
Agilent Technologies Model 1890A.

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 Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014
ISSN 1583-1078 p. 23-36

In this study, the application of a family of simplified anaerobic digestion models

(SADMs) as developed by Momoh et al., [14] in studying anaerobic digestion of cow
manure was conducted. The developed biogas yield rate models of Monod, Moser, Hills,
Andrews (Haldane) and Non-competitive Haldanes were applied in studying the
biodegradation and kinetics of biogas production from cow manure at ambient temperature.
The mathematical representation of these models is as shown in Table 1. The various model
parameters were evaluated using the solver function of the Microsoft Excel tool Pack and the
most appropriate model was selected based as its high correlation coefficient and low root
mean square error (RMSE) established between the experimental data and the predicted
specific biogas yield rate.
The highlight of these set of models, reside in their ability to use numeric values to
predict the rate limiting step of anaerobic process using the rate limiting coefficient (Af ).
Values of this coefficient greater than 0.5 implied that acetogenesis/methanogenesis was the
rate limiting step while, values of the coefficient less than 0.5 implied that
hydrolysis/acidogenesis was the rate limiting step [14].

Results and Discussion

The volatile solids content and carbon/nitrogen ratio as determined by standard

methods [16] was determined to be 66% and 22:1 respectively while, the anaerobic digestion
of the of the digesters contents lasted for a period of 35days after an initial lag phase in all
digesters. The methane content and biogas yield rate was observed to increase with increase
solid loading ranging from 2-9% (Figure 1 and Table 2). Also, the result from parameter
estimation for the five set of models tested in this study is presented in Table 3.

Table 2. Digester characteristics and biogas composition

Percent (%) Conc. Volatile Cumulative CH4 CO2
Digester pH
Total Solids solids(g/l) biogas(mL) (%) (%)
A1 2 13.48 7.300.03 94.36122 073 933
A2 3 20.43 7.350.02 173.410 143 863
A3 4 27.52 7.370.04 264.912 264 744
A4 5 34.76 7.380.02 341.39 323 683
A5 6 42.16 7.400.02 423.513 442 562
A6 7 49.76 7.600.03 516.417 483 523
A7 8 57.36 7.620.02 647.512 504 484
A8 9 65.38 7.680.02 772.910 514 494

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

Table 1. Simplified biogas yield rate models (SADMs) and corresponding growth models
Biogas yield Biogas yield rate Kinetic growth
rate model model Equations model Equations
Rmax S o
R= max S h
Monods kS =
+ So ks + Sh
A f (b R f )
based n

m
Rmax S o
R= max Sh m
Mosers kS =
+ So
m
ks + Sh
(b R )
based m
m mn
Af f
m
Rmax S o
R= max S h m
Hills based ks
m
=
+ So
m
k m n + Sh
m

Af
m
(b R ) f
mn

R max S 0 max S h
R = =
( )(A ( ) (b R ) )
Haldane
kS S 2 n
S h2
+
(Andrews)
So +
0 f s f
Sh + ks +
based A f ( s ) (b R f )
n
ki ki
Rmax So A f (s ) (b R f ) max S h
n
Non-
R = =
competitive So Af ( s ) (b R f )
(k )
n

+ So Af (s ) (b R f ) 1 +
Sh
(Haldane) n (k S + S h ) 1 +
based S
ki ki

where, Af = rate limiting step coefficient for fast substrate utilization; As = rate limiting step coefficient for very
slow substrate utilization; Af(s) = rate limiting step coefficient for fast or very slow substrate utilization; b =
fraction of initial volatile solids remaining in effluent; ks = Monods half saturation constant for acidified
substrate (g/l); Ks = Monods half saturation constants in volatile solids equivalents (g/l); kn = Hills half saturation
constant for acidified substrate (g/l); Kn = Hills half saturation constant in volatile solids equivalents (g/l); ki =
substrate inhibition constant for acidified substrate (g/l); m = coefficient of acetogenic/methanogenic bacteria
adaptation for cooperativity; n = coefficient of acidogenic bacteria adaptation for complex substrate degradation;
Rf = recalcitrant fraction; Rmax = maximum specific biogas yield rate (mL/g VS/day); R =specific biogas yield
rate (mL/g VS /day); So = initial volatile solids concentration (g/l); Sh = concentration of acidified substrate
generated (g/l); = bacteria growth rate (/day); max = maximum bacteria growth rate (/day)
max = maximum bacteria growth rate (/day); VS= volatile solids

A set of simplified anaerobic digestion models (SADMs) were used to describe the
kinetics and biodegradability of cow manure and the parameters that were estimated or
evaluated to include the following;
(a) Monod half saturation constant for the hydrolyzed and acidified substrate (ks) (g/l).
(b) Monod half saturation constant in volatile solids equivalent (Ks) (g/l).
(c) Hills half saturation constant for the acidified substrate (kn) (g/l).
(d) Hills half saturation constant in volatile solids equivalents (Kn) (g/l).
(e) Maximum specific biogas yield rate (Rmax) (mL/g VS/day).

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 Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014
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Figure 1. Experimental biogas yield and rate production with volatile solids concentration

Table 3. Parameter estimate for developed biogas yield rate models

mL/gVS/da

Biogas yield
ks kn ki
rate KS Kn m n Rf b Af(s) RMSE
Rmax

g/l (g/l) (g/l)

models
y

Monod based 1.54 0.699 - - 43 - - 1.48 0.383 0.461 0.177 9.59E-03

Mosers based 1.957 0.41 - - 34 - 0.657 1.839 0.353 0.618 0.135 8.71E-03
Hillsbased 1.957 - 0.163 - - 21.9 0.657 1.28 0.433 0.578 0.088 8.71E-03
Haldane (Andrew)
1.54 1.8E-07 - 2.6 11.23 - - 2.33 0.487 0.513 7.9E-09 9.59E-03
based
Non-competitive
1.54 5.6E-06 - 373.6 12.4 - - 0.012 0.414 0.624 4.6E-07 9.59E-03
Haldane based
kS kn
KS = Kn =
Af (b R f ) Af (b Rf )
n n

(g/L) (g/L)

(f) The coefficient m

(g) The coefficient n
(h) Fraction of volatile solid remaining in effluent (b)
(i) The recalcitrant fraction (Rf).
(j) Fraction of biodegradable volatile solids (1-Rf)
(k) Fraction of biodegradable volatile solids remaining in effluent (b-Rf)
(l) Biodegradability (1-b)
(m) Rate limiting coefficient for fast or very slow uptake of acidified substrate (Af(s))
The kinetic and biodegradability parameters were evaluated using non-linear
regression implemented via the Solver function of the Microsoft Excel tool pack and the

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

results for the estimated parameters are presented in Table 2. The appropriateness of a
particular model in describing the anaerobic process was reflected on the models ability to
produce a high correlation coefficient and low root mean square error (RMSE).
Although the five models tested provided correlation coefficient of 0.996 each, the
Moser and Hills based biogas yield rate models showed lower root mean square errors
(RMSE) of 0.00871 each, when compared to other models. Thus, the Moser and Hills based
biogas yield rate models were selected as most appropriate to describe biogas production rate
from cow manure at ambient temperature condition. Hence, further discussions were limited
to the Moser and Hills biogas yield rate models.
It is important to note that the growth models of Moser and Hills are homologue that
incorporates a coefficient m which differentiates them from the Monods growth model.
However, the developed Moser and Hills based biogas yield rate models have in addition
another coefficient n. The term m is defined as coefficient of adaptation for cooperativity
by the acetogenic/methanogenic bacteria, while, the coefficient n which is described as the
degree of adaptation for complex biomass degradation by the hydrolytic/acidogenic bacteria
[14]. For values of m and n greater than unity, some level of positive adaptation for
degradation or cooperativity is implied, while values less than unity indicate low level of
adaptation for degradation or cooperativity.

Figure 2. Combined graphs of specific biogas yield rate against volatile solids concentration

Thus, by considering the Mosers biogas yield rate model, the Monod half saturation
constants for the acidified substrate (ks) and the Monod half saturation constant in volatile
solid equivalent (Ks) were estimated to be 0.41 and 34g/l respectively. This estimated Monod

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 Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014
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half saturation constant for the acidified substrate (ks) is consistent with the half saturation
constant range of 0.1 - 0.41g/l displayed by acetoclastic methanogens reported by Pavlostathis
and Giraldo & Gomez [17]. Furthermore, by considering the Mosers biogas yield rate model,
the biodegradability parameters estimated revealed that the recalcitrant fraction in this
biomass mixture was 0.353 of the initial volatile solids fed, and the biodegradable fraction (1-
Rf) was 0.647 of the initial volatile solids fed. The biodegradability (1-b) was 0.382 while the
biodegradable fraction remaining (b-Rf) was 0.265 of the initial volatile solids fed at ambient
temperature conditions.
The coefficients of adaptation for degradation by acidogenic bacteria (n) when
considering the Moser based biogas yield rate models were 1.839 and because n was greater
than unity, some degree of acidogenic bacterial adaptation for degrading the complex biomass
was implied. The coefficient of adaptation for cooperativity by the acetogenic/methanogenic
bacterial (m) was estimated to be 0.657. However, because the value for m was less than
unity, the degree of adaptation for cooperativity by the acetogenic/methanogenic bacteria was
very poor. The reason for the poor cooperativity observed by the acetogenic/methanogenic
bacteria may not be far-fetched from the established problem of ammonia inhibition usually
associated with digestion of cow manure. Ammonia which is produced during degradation of
cow manure has been implicated in inhibiting methanogenesis [8]. In addition, the rate
limiting step for the anaerobic process by considering the Mosers based biogas yield rate
model was estimated to be 0.135 which was lower than 0.5 hence, hydrolysis was suggested
to be the rate limiting step. This is consistent with the report of Eastman and Ferguson [18]
that considered hydrolysis as rate limiting step for complex biomass.
However, by considering the Hills based biogas yield rate model, the Hills half
saturation constant for the hydrolyzed and acidified substrate (kn) was estimated to be 0.163.
This estimated Hills half saturation constant for the hydrolyzed and acidified substrate (kn)
compares reasonably with values of 0.143-0.207g/l reported by Barthakur et al., [11] for half
saturation constant for acetate by the methanogenic bacteria population. Also, this value lies
within the range of 0.1- 0.41g/l reported by Pavlostathis and Giraldo, Gomez [17] as half
saturation constant displayed by acetoclastic methanogens. In addition, the Hills half
saturation constant in volatile solid equivalents was evaluated to be 21.9g VS/l which
compares reasonably to the value of 24gCOD/l and 26g VS/l reported by Ghaly et al., [19]
and Bartharkur et al., [11] for cow manure respectively.

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

Moreover, by considering the Hills based biogas yield rate model, the recalcitrant
fraction (Rf) was estimated to be 0.433 which is close to 0.400 reported by Barthakur et al.
[11] and Hashimoto [20] for cow manure. In addition, the biodegradable fraction (1-Rf) was
calculated to be 0.567 of the initial volatile solids fed while the biodegradability (1-b) was
calculated to be 0.422 which is close to 0.46 for the biodegradability of cow manure reported
by Hussain [21] while the biodegradable fraction remaining in the effluent (b-Rf) was
calculated to be 0.145 of the initial volatile solids concentration.
In addition, the coefficient of adaptation for degradation by acidogenic bacteria (n)
when considering the Hills based biogas yield rate models was 1.28, while the coefficient of
adaptation for cooperativity by the acetogenic/methanogenic bacterial (m) was estimated to be
0.657. Again, because n was greater than unity, some degree of acidogenic bacterial
adaptation for degrading the complex biomass was implied. However, the value for m was
less than unity implying that the degree of adaptation for cooperativity by the
acetogenic/methanogenic bacteria was very poor. Similar reasons as discussed earlier may be
attributed to this low value of m.
Moreover, the rate limiting step for the anaerobic process considering the Hills based
biogas yield rate model was estimated to be 0.088 which was lower than 0.5. Thus, hydrolysis
was suggested to be the rate limiting step which is consistent with the report of Eastman and
Ferguson [18] that considered hydrolysis as rate limiting step for complex biomass.

Application of Maximum Specific Biogas Yield Rate (Rmax) for further Model
Selection
The models of Moser and Hills biogas yield rate model has been established to be
most appropriate for modelling biogas production rate from cow manure at ambient
temperature conditions both producing an estimate of 1.957ml/g VS/day as maximum biogas
yield rate (Rmax) which is close to value of 1.75ml/g VS/day reported by Budiyono et al., [22]
for anaerobic digestion of cow manure at room temperature. However by considering
definition of half saturation constant, it was observed that further model selection could be
made by comparing the half saturation constant obtained from the non-linear regression and
that obtained from graphical definition of half saturation constant.
By definition, the half saturation constant is described as substrate concentration
corresponding to 0.5Rmax. From Figure 3, it was observed that the substrate concentration

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 Leonardo Electronic Journal of Practices and Technologies Issue 24, January-June 2014
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corresponding to 0.5Rmax was 22gVS/l which was similar to the half saturation constant of
21.9gVS/l in volatile solids equivalent obtained by considering the Hills based biogas yield
rate model. Thus, the Hills based biogas yield rate model was selected over the Mosers
biogas yield rate model which estimated the half saturation constant in volatile solids
equivalent to be 34gVS/l.

Figure 3. The Moser and Hills biogas yield rate plots against volatile solids concentration

Performance Evaluation of Anaerobic Process

The process of digestion of cow manure is usually complicated because of the problem
free ammonia inhibition of acetogenesis/methanogenesis. Hence, anaerobic digestion of cow
manure is most likely to proceed sub-optimally operating below 100%. An attempt to evaluate
the performance for the digestion of cow manure at ambient condition was conducted by
plotting of a graph of (R/Rm) versus initial volatile solids substrate concentrations at varying
rate limiting step (Af) using the Hills based biogas yield rate model as shown in Figure 4. It is
clear from Figure 4 that the efficiency of the anaerobic process at total solids concentration of
9% corresponded to 66% for rate limiting step coefficient of 0.088 estimated in this study. In
essence, the expected biogas yield rate at this solid loading would be 0.66*Rmax or 1.30 ml/g
VS/day which correspond to that obtained experimentally.
In addition, from Figure 4, it was observed that as the value of the rate limiting
coefficient (Af) increased, the performance of the anaerobic process improved. In essence,
conditions which increase the rate limiting coefficient (Af) that is, improve the hydrolysis rate
(e.g. pulverization) can lead to improvement in performance of anaerobic process especially
for volatile solid concentration ranging from 20-100gVS/l. This finding is consistent with that

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 Application of Simplified Anaerobic Digestion Models (SADMs) for Studying the Biodegradability and
Yusuf O.L. MOMOH and Benedict ANYATA

reported by Palmowski et al., [23] who observed an increase in biogas yield during
mechanical treatment of complex biomass.

Figure 4. Plot of efficiency of anaerobic process against volatile solids

Conclusions

In this study, the anaerobic breakdown of cow manure and biogas yield production
rates were effectively described using the simplified anaerobic digestion models, however,
only the Hills based biogas yield rate model was ultimately selected as most appropriate for
describing the anaerobic biodegradability and kinetics of cow manure at ambient temperature.
The recalcitrant fraction in cow manure was estimated to be 0.433, the biodegradable fraction
0.578; while the biodegradability of cow manure was estimated to be 0.422. The half
saturation constant in volatile solids equivalent was determined to be 21.9g VS/l. In addition,
the rate limiting step coefficient was determined to be 0.088 which implied
hydrolysis/acidogenesis as the rate limiting step.

Acknowledgements
This research was supported by the Petroleum Technology Development Fund Local
Scholarship Scheme (Grant Number PTDF/TR/lS/MOLY/215/54) Nigeria.

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